High performance thermoplastic

ABSTRACT

A high performance thermoplastic hose useful as a power steering hose, the high performance thermoplastic hose comprising a high performance engineering thermoplastic such as polyurethane and a chlorine-containing polyolefin such as chlorinated polyethylene, chlorinated polypropylene, chlorinated copolymers containing ethylene and propylene, chlorosulfonated polyethylene, chlorosulfonated polypropylene, chlorosulfonated copolymers of ethylene and propylene or mixture thereof, is disclosed. Also disclosed are a method for manufacturing the high performance thermoplastic hose, and a thermoplastic vulcanizate capable of resisting chemical attack and withstanding temperatures up to about 300° F.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 10/262,795, filedOct. 2, 2002, now U.S. Pat. No. 6,623,822, which is a continuation ofU.S. Ser. No. 09/311,310, filed May 13, 1999, now U.S. Pat. No.6,524,673. U.S. Ser. No. 10/262,813, filed Oct. 2, 2002 concurrentlywith U.S. Ser. No. 10/262,795, is a divisional of U.S. Ser. No.09/311,310, filed May 13, 1999, now U.S. Pat. No. 6,524,673, and is alsoa related application.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a thermoplastic vulcanizate preparedfrom a high performance engineering thermoplastic polymer such aspolyurethane and a chlorosulfonated polyolefin and/or a chlorinatedpolyolefin; to a high performance hose such as a power steering hoseconstructed from such thermoplastic vulcanizate material; and to amethod for the manufacture of such high performance hoses.

2. Description of the Prior Art

Hoses, particularly curved hoses, typically, are manufactured bypositioning a precut length of uncured hose over a curved mandrel andthen heating the mandrel and curing the hose so that the hose retainsits desired shape. The hose may solely be an elastomeric tube or it maybe surrounded or have incorporated therein a twined reinforcement.Optionally, a cover may surround the hose. Typically, the hose is madeby extruding a tube of heat curable elastomer. The hose is then placedover the mandrel which is heated to cure the inner layer next to themandrel. The cured hose is then removed from the mandrel while themandrel is hot to facilitate easy removal of the cured hose from themandrel. One such method is described in U.S. Pat. No. 4,537,736 toPeltzman et al. Such rubber hoses have been used in a wide variety ofapplications such as fuel feed hoses, torque converter hoses, airconditioner hoses, power steering hoses, etc. However, in general,rubber surfaces do not exhibit high resistance to chemical attack andprior art attempts have failed to increase the chemical resistancebeyond certain limits. For example, U.S. Pat. No. 5,476,121 to Yoshikawaet al discloses rubber hoses having improved barrier and flexibilityperformance by providing an inner tube of a synthetic resin having anouter peripheral surface, forming a thin film of silver or a silver basealloy on the outer surface of the inner tube, and heat curing a rubberlayer to the thin film through an adhesive layer.

High performance hoses such as power steering hoses require highresistance to both chemical and temperature degradation. At present,power steering hoses and other high performance hoses are made fromcompounded elastomers such as a chlorinated polyethylene, achlorosulfonated polyethylene or similar materials capable ofwithstanding temperatures up to 300° F. and the chemical effects ofpower steering fluids. Chlorine-containing polyolefins includingchlorinated polyethylene and chlorosulfonated polyethylene generallypossess good mechanical properties, good compression set, good lowtemperature flexibility and good dynamic fatigue resistance. Thesematerials also exhibit excellent aging, weathering, chemical and ozoneresistance due to their saturated backbones. However, in order towithstand high temperatures of about 300° F. and chemical resistance topower steering fluids, hoses constructed of such materials must be builtand vulcanized on a mandrel and then removed from the mandrel foradditional processing. A method for the manufacture of power steeringhose on a mandrel is further described in U.S. Pat. No. 3,972,757 toDerderian et al. In view of the cost associated with manufacturing highperformance hoses such as power steering hoses, it is desirable toprovide materials having the desired characteristics but which areeasily formable without the use of a mandrel while providing improvedperformance and reduced overall costs.

U.S. Pat. No. 5,683,773 to Kemper teaches an automotive hose where theinner tube or, preferably, the cover portion is formed of an elastomercomprising a chlorinated polyethylene-based elastomer or polyether-basedelastomer stabilized with barium sulfate.

SUMMARY OF THE INVENTION

In accordance with the present invention, high performance hoses such aspower steering hoses are prepared from a thermoplastic vulcanizate (TPV)using a chlorinated polyolefin and/or a chlorosulfonated polyolefin withpolyurethane or one or more similar high performance engineeringthermoplastic materials. There is no known thermoplastic material, whenused alone, which will withstand the temperature and the fluid of powersteering applications for prolonged periods of time. However, it hasbeen found that such thermoplastic materials typically have high greenstrength, high tear strength and good abrasion resistance and when usedwith the chlorinated polyolefins and/or chlorosulfonated polyolefins inaccordance with the present invention, can be employed in themanufacture of high performance hose such as power steering hose. Thehigh performance engineering thermoplastic material can be crosslinkedin the matrix during extrusion of the thermoplastic vulcanizate byadding any suitable crosslinking agent to the vulcanizate.Chlorosulfonated polyethylene or a mixture of chlorinated polyethyleneand chlorosulfonated polyethylene compounded with polyurethane has beenfound to be particularly useful in the preparation of the thermoplasticvulcanizate of the present invention. The thermoplastic vulcanizate ofthe present invention exhibits the following advantages over the priorart:

-   -   (1) Vulcanization is not required;    -   (2) The material can be extruded to close tolerance without a        mandrel;    -   (3) The material is light weight due to high modulus, and less        material is needed;    -   (4) The material is recyclable;    -   (5) The material is easily formed into hoses;    -   (6) The material has better abrasion and tear resistance than        prior art materials; and    -   (7) The material can be made at a lower overall cost with better        performance than prior art materials.

It is one aspect of the present invention to provide a light weightthermoplastic vulcanizate material having improved abrasion and tearresistant characteristics for use in the manufacture of high performancehoses such as power steering hoses.

It is another aspect of the invention to provide a high performance hosesuch as a power steering hose constructed from such thermoplasticvulcanizate material.

It is yet another aspect of the invention to provide a method formanufacturing the high performance hose which eliminates the processingsteps required for prior art elastomeric hose.

DETAILED DESCRIPTION OF THE INVENTION

The thermoplastic vulcanizate material of the present inventioncomprises a chlorinated polyolefin and/or a chlorosulfonated polyolefinand a high performance engineering thermoplastic material such aspolyurethane. It has been found that the present thermoplasticvulcanizate is particularly useful in the manufacture of highperformance hoses. In a preferred aspect of the invention, thethermoplastic vulcanizate is used as the matrix for the construction ofpower steering hoses in automobiles.

The chlorine-containing component useful in the present invention is achlorinated polyolefin or a chlorosulfonated polyolefin and includes,but is not limited to, chlorinated polyethylene, chlorinatedpolypropylene, chlorosulfonated polyethylene, chlorosulfonatedpolypropylene, chlorinated copolymers of ethylene and propylene,chlorosulfonated copolymers of ethylene and propylene and mixturesthereof.

The chlorine-containing polyolefin component of the thermoplasticvulcanizate is a mixture of two or more member selected from the groupconsisting of chlorinated polyethylene, chlorinated polypropylene,chlorinated copolymers of ethylene and propylene, chlorosulfonatedpolyethylene, chlorosulfonated polypropylene, and copolymers ofchlorosulfonated ethylene and chlorosulfonated propylene, with theproviso that mixtures of chlorinated polyethylene and chlorosulfonatedpolyethylene; mixtures of chlorinated polyethylene, chlorinatedpolypropylene and chlorinated copolymers of ethylene and propylene; andmixtures of chlorosulfonated polyethylene, chlorosulfonatedpolypropylene; and chlorosulfonated copolymers of ethylene and propyleneare excluded. For the purpose of this invention, the term copolymer isintended to include two or more monomers such as ethylene, propylene,butenes, etc. Hypalon, a chlorosulfonated polyethylene available fromDuPont has been found to be particularly useful in the presentinvention.

The amount of chlorinated polyolefin and/or chlorosulfonated polyolefinin the thermoplastic vulcanizate is typically in the range of about 10to 90% by weight of the thermoplastic vulcanizate, and preferably, about30 to 70% by weight of the thermoplastic vulcanizate. While each of thechlorinated polyolefin and the chlorosulfonated polyolefin can be usedwith the exclusion of the other in the present invention, it has beenfound that a combination of the chlorinated polyolefin and thechlorosulfonated polyolefin provides excellent results as well. Whenboth chlorinated polyolefin and chlorosulfonated polyolefin are presentin the thermoplastic vulcanizate, the ratio of chlorinated polyethyleneto chlorosulfonated polyethylene typically will be about 3:1 to 1:3,preferably about 2:1 to 1:2 and most preferably about 1:1. As indicatedearlier Hypalon, a chlorosulfonated polyethylene manufactured by DuPont,has been found to be particularly useful as the chlorosulfonatedcomponent.

The high performance engineering thermoplastic component of thethermoplastic vulcanizate can be any of the high performance engineeringthermoplastic materials commonly used in the industry. Examples of suchhigh performance engineering plastic materials include polyurethanes;and may include polyethers such as polyacetal, polyphenylene oxide,polyether ketone, polyphenylene sulfide, etc.; polyamides such as nylon,e.g., nylon 6, nylon 66, nylon 4, nylon 11, nylon 12, nylon 6/12, nylon6/10, etc.; highly aromatic polyamides such as Kevlar and Nomex whichare available from DuPont; polyesters, such as polyethyleneterephthalate; copolyesters such as Hytrel available from DuPont;polyimides, such as polyether imides, polyimide imides,polybismaleimides; polysulfones and the like. These resins may be usedalone or as a blend of two or more of the resins. Preferably, thethermoplastic component is polyurethane. The amount of the highperformance engineering thermoplastic component present in thethermoplastic vulcanizate will be that which is sufficient to providethe improved characteristics of the vulcanizate. The amount of the highperformance engineering thermoplastic component can be in the range ofabout 90 to 10% by weight based on the weight of the thermoplasticvulcanizate and, preferably, about 70 to 30% by weight based on theweight of the thermoplastic vulcanizate.

Optionally, the high performance engineering thermoplastic material maybe crosslinked in the thermoplastic vulcanizate matrix by adding asuitable crosslinking agent to the vulcanizate prior to or duringextrusion of the high performance hose. The thermoplastic vulcanizate ofthe present invention may be crosslinked with conventional crosslinkingsystems such as peroxides, e.g., dicumyl peroxide,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy) hexyne-3,1,1-bis(t-butylperoxyne)-3,t-butylperoxybenzoate, and the like. It is believed that thethermoplastic vulcanizate of the present invention may also becrosslinked with polyols such as aromatic and cyclic polyols, e.g.,hexafluoroisopropylidene-bis-(4-hydroxyphenyl) hydroquinone,isopropylidene-bis-(4-hydroxyphenyl), etc.; polyamines such ashexamethylenediamine carbamate, alicyclic diamine carbamate,dicinnamilidene hexamethylenediamine, and the like; cyanurates such astriallyl cyanurate (TAC); isocyanurates such as triallyl isocyanurate(TAIC); and the like; isocyanates and diisocyanates, such asdiphenylmethane diisocyanate. Crosslinking agents containing at leasttwo and preferably more than two functional groups such as TAC, TAIC,isocyanates, mixtures of isocyanates and polymeric isocyanates havingfunctionality of more than 2.0 are found to be very useful. In somecases a conventional crosslinking accelerator may be used to provideimproved results. Typically, the crosslinking agent will be added to thevulcanizate in an amount of about 1 to 10% and preferably about 1 to 5%by weight, based upon the weight of the vulcanizate.

The thermoplastic vulcanizate of the invention is particularly useful inthe manufacture of high performance hoses such as power steering hosesand, in addition to being able to withstand the adverse effects of hightemperature and chemical degradation, the present materials do notrequire vulcanization on a mandrel as is commonly required in the priorart; they can be extruded to close tolerance; they are light weight andrecyclable, and they have better abrasion and tear resistance than priorart materials.

Other additives such as carbon black; silica; calcium carbonate; clay;diatomaceous earth, mica; heat stabilizers, e.g., metal oxides such asmagnesium oxide, organotin compounds, and mixed metal salts;antioxidants; lubricants; plasticizers, softeners, processing aids; andthe like may be incorporated into the thermoplastic vulcanizate inamounts generally known in the art to provide the desired effect forwhich they are added.

According to the invention, the high performance hose can be formed toclose tolerance by a simple extrusion process wherein the thermoplasticvulcanizate is prepared by dynamic vulcanization where the elastomericcomponent is vulcanized during mixing.

The following examples are submitted for the purpose of furtherillustrating the present invention and are not intended as a limitationon the scope thereof.

EXAMPLE

Thermoplastic vulcanizates (TPV) are made with polyurethane andchlorosulfonated polyethylene or a mixture of chlorosulfonatedpolyethylene and chlorinated polyethylene by dynamic vulcanizationmethod wherein the vulcanizate contains about 30 to 70% polyurethane andabout 70 to 30% chlorosulfonated polyethylene or a mixture ofchlorosulfonated polyethylene and chlorinated polyethylene wherein theratio of chlorosulfonated polyethylene to chlorinated polyethylene isabout 3:1 to 1:3. The compounds are extruded to a tight tolerance tube,braided with or without adhesive to get proper adhesion and then coveredwith the same or different composition TPV using the same basematerials. The hoses are then cut into desired length, formed internallyor externally by heating the fixture in a continuous line passingthrough an oven, and cooling the fixture by a suitable method,preferably by dipping or spraying using cold water.

Although the invention has been described and exemplified herein withrespect to the preferred embodiments thereof, it is to be understoodthat the invention is not limited to the embodiments, and thatvariations can be made therein without departing from the scope of theinvention.

1. An extruded high performance, chemical resistant hose, whichwithstands temperatures up to about 300° F. for prolonged periods oftime, said extruded high performance, chemical resistant hose having amatrix comprising a thermoplastic vulcanizate comprising: 1) athermoplastic polyurethane in an amount of about 30 to 70 weight % ofsaid thermoplastic vulcanizate; 2) a chlorine-containing polyolefin inthe amount of about 70 to 30 weight % of said thermoplastic vulcanizate,wherein said chlorine-containing polyolefin is a mixture of two or moremembers selected from the group consisting of A, B, C, D, E, E, and F,wherein A is chlorinated polyethylene, B is chlorinated polypropylene, Cis chlorinated copolymers of ethylene and propylene, D ischlorosulfonated polyethylene, E is chlorosulfonated polypropylene, andF is chlorosulfonated copolymers of ethylene and propylene, with theproviso that mixtures of A & B; A & C; A & D; B & C; B & D; C & D; A, B& C; A, B & D; A, C & D; and A, B, C & D are excluded; and 3) acrosslinking agent, wherein said high performance engineeringthermoplastic polyurethane is crosslinked in said matrix.
 2. Theextruded high performance, chemical resistant hose of claim 1 whereinsaid chlorinated polyolefin is a mixture of chlorosulfonatedpolyethylene and chlorosulfonated polypropylene.
 3. The extruded highperformance, chemical resistant hose of claim 1 wherein said chlorinatedpolyolefin is a mixture of chlorinated polyethylene and chlorosulfonatedpolypropylene.
 4. The extruded high performance, chemical resistant hoseof claim 1 wherein said chlorinated polyolefin is a mixture ofchlorosulfonated polypropylene and a chlorinated copolymer of ethyleneand propylene.
 5. The extruded high performance, chemical resistant hoseof claim 1 wherein said chlorinated polyolefin is a mixture ofchlorinated polyethylene and a chlorosulfonated copolymer of ethyleneand propylene.
 6. The extruded high performance, chemical resistant hoseof claim 1 wherein said chlorinated polyolefin is a mixture ofchlorinated polypropylene and a chlorosulfonated copolymer of ethyleneand propylene.
 7. The extruded high performance, chemical resistant hoseof claim 1 wherein said chlorinated polyolefin is a mixture ofchlorosulfonated polyethylene and a chlorosulfonated copolymer ofethylene and propylene.
 8. The extruded high performance, chemicalresistant hose of claim 1 wherein said chlorinated polyolefin is amixture of chlorosulfonated polypropylene and a chlorosulfonatedcopolymer of ethylene and propylene.
 9. The extruded high performance,chemical resistant hose of claim 1 wherein said thermoplasticpolyurethane is crosslinked in said matrix by dynamic vulcanizationduring the manufacture of said hose.
 10. The extruded high performance,chemical resistant hose of claim 1 wherein said crosslinking agent isselected from the group of a peroxide, an isocyanate having afunctionality of more than 2.0, a polyisocyanate having a functionalityof more than 2.0, a polyamine containing two or more functional groups,a polyol containing two or more functional groups, and mixtures thereof.11. The extruded high performance, chemical resistant hose of claim 1wherein said hose is an automotive power steering hose.
 12. The extrudedhigh performance, chemical resistant hose of claim 1 wherein saidchlorinated polyolefin is a mixture of chlorinated polypropylene andchlorosulfonated polypropylene.
 13. The extruded high performance,chemical resistant hose of claim 1 wherein said chlorinated polyolefinis a mixture of a chlorinated copolymer of ethylene and propylene and achlorosulfonated copolymer of ethylene and propylene.